Apparatus for producing oxygen and/or hydrogen in an environment devoid of breathable oxygen

ABSTRACT

An apparatus for producing oxygen in an atmosphere substantially devoid of breathable oxygen.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application Ser. No. 60/967,756 filed Sep. 7, 2007, which is herein incorporated by reference.

FIELD OF THE INVENTION

The present invention relates to an oxygen generating apparatus comprising oxygen-delivering chemical chamber within a unit coupled to a filter material for generating oxygen from water and air to be used in an atmosphere void of oxygen. The water used to produce oxygen can be either exhaled water vapor, water generated from purification of urine, and/or on board drinking supplies.

BACKGROUND OF THE INVENTION

The present invention relates in general to a chemical based oxygen-generating apparatus and in particular to a new and useful respirator which includes an oxygen generating chemical chamber coupled to a cartridge comprising a filter material for liberating oxygen from water. The chemical chamber is arranged so that oxygen generated from the chemical chamber flows to the filter material of the present invention. In addition, the cartridge containing the filter material of the present invention is arranged in the apparatus so that the respiration path of exhaled air from a person flows over the filter material and oxygen generated by the filter material flows back into the inhalation pathway of the person.

Chemical oxygen generators are typically used in situations requiring emergency supplemental oxygen, such as in aviation, during decompression, in mine rescue operations, in submarines, and in other similar settings. Chemical oxygen generating compositions based upon the decomposition of alkali metal chlorates or perchlorates have long been used as an emergency source of breathable oxygen, such as in passenger aircraft, for example. Oxygen for such purposes must be of suitably high purity. For example, the requirements of SAE Aerospace Standard AS8010C are frequently applicable to oxygen used for breathing in aviation applications.

Chemical oxygen generators available on the market today commonly utilize sodium chlorate, potassium perchlorate, and lithium perchlorate as sources of oxygen. Upon decomposition, the chlorate or perchlorate releases oxygen. In a typical chemical oxygen generator, a sodium chlorate candle is encased in a stainless steel canister, and oxygen is generated by decomposition of sodium chlorate in the presence of a commonly used fuel, such as iron powder, to provide extra heat to sustain the decomposition. However, these oxygen generators also release toxic chlorine gas, up to several hundred ppm, through side reactions and some organic contamination. The toxic chlorine gas generated along with oxygen must be removed in order to make the oxygen breathable.

Filters often used to absorb the chlorine gas in these oxygen-generating systems, such as cast filters or granular bed filters with hopcalite, have their own problems. For example, granular hopcalite bed filters are susceptible to damage from vibration, which can be a problem, since chemical oxygen generators in aircraft are frequently subjected to vibration. During vibration, the granules abrade against one another, so that the particle sizes of the granules are gradually reduced, and the filter bed becomes more tightly packed, settling to the bottom of the filter bed and creating channels that can lead to failure of the filter. In order to avoid the effects of abrasion, settling and channeling, the filter bed is usually loaded as several layers of hopcalite granules with ceramic fiber or glass fiber pads in between the hopcalite layers. However, it is difficult to pack the layers of hopcalite evenly inside the filter compartments, and the assembly process is typically slow and tedious. The filter pads in between the hopcalite layers further increase the overall weight of the filter making them expensive and very heavy. This makes personal use less likely.

Other chemical oxygen generating devices available on the market today do not use perchlorates and therefore do not produce chlorine gas. However, these also have problems. For example, barium peroxide, lithium peroxide and calcium hydroxide have been used together with cobalt oxide as inhibitors to moderate the performance of sodium chlorate in oxygen generating compositions. However, barium peroxide is toxic, so that disposal of expended and scrap oxygen generators containing barium peroxide can be expensive. Lithium peroxide and calcium hydroxide are very strong inhibitors, so that only small quantities, such as a fraction of one percent in the oxygen generating compositions, for example, can be used, making it relatively difficult to uniformly distribute the inhibitors in the oxygen generating compositions. Lithium peroxide also tends to cake when it adsorbs moisture and carbon dioxide, making mixing even more difficult. For a formulation containing cobalt oxide as a catalyst and lithium peroxide or calcium hydroxide as an additive, a prolonged and thorough mixing is critical to reduce the variation within each lot, and from one lot to the next. Decomposition of calcium hydroxide also produces water which can be undesirable for some applications. Calcium hydroxide also has minimal catalytic activity when no other catalyst is present.

Since calcium hydroxide is a relatively strong inhibitor, in oxygen generating compositions formulated with cobalt oxide and calcium hydroxide, localized regions having a high cobalt oxide concentration and a low calcium hydroxide concentration occur due to imperfect mixing, and have a far higher decomposition rate than other localized regions with a low cobalt oxide and a high calcium hydroxide concentration. Lithium hydroxide and calcium hydroxide based formulations of oxygen generating compositions thus typically exhibit a relatively high variation of performance within and among lots, due to non-uniform distribution of the ingredients within the oxygen generating compositions.

Therefore, what is needed is an oxygen-generating device that is able to produce consistent, amble amounts of oxygen in a device that does not require large heavy filters/machinery and does not produce toxic by-products that must be removed or are difficult dispose. The present invention provides a chemically assisted oxygen-generating apparatus that overcomes the shortcomings of the prior art and is truly portable oxygen generating system capable of maintaining proper oxygen levels necessary for breathing by a patient. The present invention is discussed in the section below.

SUMMARY OF THE INVENTION

One object of the present invention is to provide a breathing device that is able to produce breathable oxygen in atmospheres that are devoid of oxygen.

Another object of the present invention is to provide a portable breathing device that produces breathable oxygen that does not require bulky, heavy components so that the device can be truly portable. That is, that present invention provides an apparatus for producing oxygen and/or hydrogen gas in an atmosphere devoid of oxygen gas using a chemical chamber coupled to a filter material that is able to generate oxygen from water.

Yet another object of the invention is to provide a breathing device that is able to produce breathable oxygen in atmospheres that are devoid of oxygen by utilizing water purified from urine in conjunction with chemically generated oxygen. This type of device can be used in space exploration where urine is contained within a space suit and is readably available to produce water for oxygen generation as the condensation water vapor of exhaled air.

Still yet another objective of the present invention is to provide a method for producing oxygen in an atmosphere devoid of oxygen using the apparatus of the present invention.

One embodiment of the present invention provides an apparatus for producing oxygen gas in an environment substantially devoid of oxygen comprising a housing assembly separated into two chambers. The first chamber comprises a plurality repeating catalytic, ultra filtration and hydrogen peroxide generating screens in communication with a tubular and solid frame. The repeating units are arranged in an alternating pattern and comprise in general a diRuthenium/diRuthenium catalytically active screen for splitting water into bimolecular oxygen and hydrogen, a zeolite-containing screen for ultra filtration of bimolecular oxygen and a diRuthenium/diRuthenium/zeolite containing screen for generating hydrogen peroxide. The second chamber separated from the first chamber by a separator comprises a catalyst, such as MnO₂, that generates oxygen upon interaction with a liquid reactant such as hydrogen peroxide.

The repeating unit of the first chamber comprises a porous boron doped carbon film comprising diRuthenium/diRuthenium molecules and at least one type of electronegative ion. The diRuthenium/diRuthenium molecules and electronegative ions are in direct contact with the porous boron doped carbon film. The porous boron doped carbon film further comprising a nanocarbon tubular mesh network and a Ruthenium ion capturing siderophore plate or hollow tube that is connected to the opposite surface of the porous boron doped carbon film in which the diRuthenium/diRuthenium molecules are attached. The siderophore plate/hollow tube is ionically charged so as capture free Ruthenium ions that become dislodged from the porous boron doped carbon film.

Proximal to the diRuthenium/diRuthenium screen and facing the surface of the screen having the siderophore is the second screen in the series of three screens. The second screen is a synthetic film comprising a plurality of nanocarbon tubules attached and/or embedded on a surface of the synthetic film to form a nanocarbon tubule mesh network and at least one zeolite crystalline body in direct contact with the nanocarbon tubules. The synthetic film has a multiplicity of pores having a diameter of about 0.1 to about 3.0 nm and the zeolite crystalline bodies that are attached to the nanocarbon tubules overlap at least part of the pores of the synthetic film.

Proximal to the synthetic film having zeolite crystalline bodies is the final screen of the three screen-repeating unit comprising both zeolite crystalline bodies as well as diRuthenium/diRuthenium complexes. The synthetic film/zeolite together with the diRuthenium/diRuthenium complexes generate hydrogen peroxide from hydrogen and oxygen. The hydrogen and oxygen generated from either the chemical chamber or from the first and second screens of the repeating units can be used as reactants to generate hydrogen peroxide. Once generated, the hydrogen peroxide can be directed to the second chamber where it eventually reacts with the embedded catalyst so as to generate additional oxygen.

The zeolite crystalline bodies and the diRuthenium/diRuthenium complexes of the third screen of the repeating unit can be localized in a small central patch of the screen or evenly dispersed throughout. In addition, the third screen of the repeating unit can be optionally equipped with a siderophore plate so as to assure that free Ruthenium ions does not come in contact with humans.

Multiple repeating units can be arranged in series so as to provide oxygen for breathing in a rarified atmosphere in either an individual breathing device, a space suit or a defined area. In one embodiment of the present invention the repeating units can be arrange in a cartridge so that they can be replaced when their effectiveness to produce oxygen is depleted. The combination of generating oxygen from water and chemically producing oxygen from the catalytic reaction of MnO₂ and hydrogen peroxide is sufficient to condition a defined atmosphere devoid of oxygen to support the respiration of individuals without specialized equipment.

The present invention is also directed to a method for producing oxygen in a oxygen depleted or an environment devoid of breathable oxygen using the apparatus of the present invention and water or urine as a source of water.

The apparatus of the present device will be described in greater detail in the Detailed Description section in conjunction with the figures below.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows a prospective view of the front surface of the porous boron doped carbon film comprising diRuthenium/diRuthenium molecules of the filter material of the present invention.

FIG. 2 shows a prospective view of the back surface of the porous boron doped carbon film comprising diRuthenium/diRuthenium molecules and siderophore plate of the filter material of the present invention.

FIG. 3 shows a prospective view of the surface of the second screen comprising zeolite crystalline bodies of the filter material of the present invention.

FIG. 4 shows a prospective view of the surface of the third screen comprising zeolite crystalline bodies and diRuthenium/diRuthenium molecules of the present invention.

FIG. 5 shows a prospective view of the front surface of the second screen film comprising zeolite crystalline bodies set in a frame.

FIG. 6 shows a prospective view of the front surface of the screen with a flow tube connected to the frame of the filter material of the present invention.

FIG. 7 shows a cross section view of a cartridge with a flow tube connected to the frame of the screens of the present invention.

FIG. 8 shows a prospective view of the housing assembly of the present invention.

FIG. 9 shows a cross section of the housing assembly of the present invention.

FIG. 10 shows a exploded view of one repeating unit comprising three screens of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to an oxygen-generating apparatus that is able to produce breathable oxygen in a rarified oxygen environment. The apparatus of the present invention produces oxygen using both chemical generation of oxygen from hydrogen peroxide and a catalyst and the splitting of water. The apparatus of the present invention is a two-chamber system having a chemical chamber and a catalytic/filtering chamber containing repeating units that comprise alternating repeating screens.

Each repeating unit comprises three different types of screens in a specific arrangement so as to optimize the production of oxygen from water and hydrogen peroxide. The filter material of the first screen and the second screen are designed to complimentarily operate with each other so as to chemically produce bimolecular oxygen and hydrogen from water and effectively filter oxygen out of the air passed over the screen. That is, the first screen of the repeating unit catalytically splits water into bimolecular water and hydrogen and the second screen is an ultra-filtration screen proximal to the first screen which filters out the oxygen produced from splitting water in the first screen.

The third and final screen is arrange proximal to the second screen in the series and is designed to generate hydrogen peroxide from oxygen and hydrogen. This screen comprises a combination of both the zeolite crystalline bodies of the second screen and the diRuthenium complex of the first screen specifically arranged on a single screen. In this arrangement the diRuthenium complex and the zeolite crystalline bodies arranged on a single screen complement each other to provide a catalytic effect that converts hydrogen and oxygen to hydrogen peroxide. The hydrogen peroxide produced by the third screen of the repeating unit can then be used by the second chamber to produce even more oxygen.

The hydrogen peroxide that is recycled is extracted along with the generated water and the aqueous solution is purified and concentrated to the desired concentration of hydrogen peroxide to be reused again. The anthraquinone working solution is returned to the hydrogenation reactor to complete the cycle and mixtures thereof.

Multiple repeating units can be aligned in series to provide the necessary amount of oxygen required for breathing. The specific arrange and design of the screens in the alternating units prevent both the build up of radical intermediates during oxygen generation that may cause the decomposition of the oxygen generating filters as well as of the build up of excess water on the ultra filtration material of the second screen which is known to reduce the functionality of such filters.

The apparatus of the present invention is designed so that it can either be used as a portable breathing device above or below water, either in a helmet, space suit or as a stand alone unit that can be placed in an environment devoid of oxygen in order to condition the air with breathable oxygen so as to support life.

The screens of the repeating units each has a tubular and solid frame that may be is configured to fit into a cartridge or can slide directly into the helmet, space suit or stand-alone unit directly. The cartridge, if used, can be designed to accommodate a plurality of repeating units and can range in size from about less than an inch to several feet depending on the location and the amount of oxygen to be produced. In other words, the conditioning of a large cabin, such as a spacecraft may require one or more stand-alone units that have repeating units that are several feet in length.

The second chamber of the present invention comprises a catalyst deposed therein or preferably embedded within the walls of the second chamber. Supplied to the second chamber is at least one compound that generates oxygen upon interaction with the catalyst. In one embodiment of the present invention, the catalyst used in the second chamber is either manganese dioxide, silver or mixtures thereof. Other catalysts that react with hydrogen peroxide can be used in the second chamber of the invention and are envisioned to be within the scope of the present invention. MnO₂ is specifically preferred as the catalyst of the second chamber.

Urine excreted aboard transport ships contains water that can be used in the product of oxygen in the present invention. However, the water in urine also contains various electrolytes that can yield free ions such as Cl⁻ when they come in contact with certain catalyst that can be used in the second chamber of the present invention. Since MnO₂ is less apt to yield chlorine gas, hypochlorous acid, or a THM, when functioning as an electrode, water electrolysis—oxygen generation—occurs preferentially even in the presence of chloride ions, and the generation of chlorine gas or hypochlorous acid is inhibited.

MnO2 embedded within the second chamber—as catalyst vastly increases the rate of decomposition of hydrogen peroxide. If generating High strength peroxide (also called high-test peroxide, or HTP) must be stored in a vented container to prevent the buildup of pressure leading to the eventual rupture of the container. Preferably we use a lower concentration of Hydrogen peroxide preferably from 6% to 45%, more preferably at 8% thus eliminating the need for vented and high-pressure safety systems to store such volatile liquid. A common concentration for hydrogen peroxide is “20 volume”, which means that when 1 volume of hydrogen peroxide is decomposed, it produces 20 volumes of oxygen. A 20 “volume” concentration of hydrogen peroxide is equivalent to 1.67 mol/dm³ (Molar solution) or about 6%.

As stated above, the catalyst can be evenly disbursed throughout the second chamber or embedded in the walls of the second chamber. As hydrogen peroxide drips into this chamber it reacts with the catalyst to generate oxygen. In addition to hydrogen peroxide, additional compounds may be used depending on the catalyst used and are also envisioned to fall within the scope of the present invention. The hydrogen peroxide is feed to the second chamber via a hydrogen peroxide supply line which is controlled by a pump. The oxygen produced is then siphoned out of the chamber and either used for breathing (in a helmet), mixed with the oxygen generated from the repeating units and exited into the environment to be treated, or stored for later use.

In one embodiment of the present invention, the apparatus is configured to a extraterrestrial suit having a mouthpiece and/or helmet that funnels exhaled air from a patient to a tubular frame where it is distributed in such a way so as to provide a flow of air over the filter material and catalyst thin film of the repeating units of the present invention. Water vapor from exhaled air and/or from purified urine, is then chemically split into oxygen and hydrogen as it flows across/through the filter material of the present invention. The oxygen flow is then circulated back to the patient for respiration directly or is combined with the oxygen produced by the second chamber and either stored for later use or exhausted to the environment.

The first and second screens of the repeating units of the first chamber further comprise a plurality of blow-by accelerator nozzles that are in communication with the hollow portion of the frame of each screen and the overall device. The blow-by accelerator nozzles are instrumental in providing air from the surroundings to the first and second screens. In addition to the blow-by accelerator nozzles, the apparatus also contains a plurality of scavenger nozzles that are in communication with the frame and are positioned across from the plurality of blow-by accelerator nozzles. The combination of the plurality of accelerator nozzles (that are paralleled and flow air across the surface of the filter material in the filter chamber) and the plurality of scavenger nozzles (that remove un-reacted air flow, by-products and excess charge buildup from the air flow over the filter) provides a flow of air for the continued operation of the filter material and captures un-reacted air flow, by-products, oxygen and hydrogen into the frame to be used and/or vented out of the apparatus.

To facilitate the flow of air across the filter material, the blow-by accelerator nozzles can be designed to have a wide end that is attached to the frame and a narrower end positioned at least partially over the filter material so that air from the blow-by accelerator nozzles flows over the filter material. The scavenger nozzles of the present invention have the reverse design. That is, the scavenger ports can have a narrow end attached to the frame and a wide end positioned at least partially over the filter material so that un-reacted air flow and by-products from the blow-by accelerator ports is captured by the scavenger ports and channeled into the frame to be used and/or vented out of the apparatus.

In one embodiment of the present invention, the oxygen and/or hydrogen produced from both the first and second chambers can be stored in a storage vessel so that the gases can be used at later time. Here, several cartridges can be used in series so that the additional flow of air can be fully utilized and excess bimolecular oxygen can be produced. Still further, as stated above, the apparatus can be designed so that the filters generate bimolecular oxygen from water purified from urine (i.e. in low or no moisture environments such as in an extraterrestrial environment). All of these configurations are envisioned to fall within the scope of the present invention and are designed to use the catalytic and filtering screens as well as the chemical chamber of the present invention.

The first screen of the alternating filter material is a porous boron doped carbon film comprising diRuthenium/diRuthenium molecules and at least one type of electronegative ion directly attached to the carbon film. The second screen arranged proximal (in series) to the first screen is made out of a synthetic film comprising at least one zeolite crystalline body in direct contact with concentrically arranged nanocarbon tubules attached/embedded into the synthetic film. The synthetic film comprises a multiplicity of pores having a diameter of about 0.1 nm to about 3.0 nm. The zeolite crystalline bodies are attached to the nanocarbon tubules and overlap at least a portion of the pores. It is this structure that makes up a single repeatable unit and can be placed in series to generate high out of oxygen from a given source.

The synthetic film comprises a multiplicity of pores having a diameter of about 0.1 to about 3.0 nm. The zeolite crystalline bodies are attached to the nanocarbon tubules and overlap at least a portion of the pores. It is this structure that makes up a single repeatable unit and can be placed in series to generate high oxygen output form water vapor from exhaled air or another source.

The unique diRuthenium/diRuthenium molecule used in the first screen contains several Ruthenium atoms. Chemically “Ruthenium” is generally found in ores with the other platinum group metals in the Ural Mountains and in North and South America. Small but commercially important quantities are also found in pentlandite extracted from Sudbury, Ontario and in pyroxenite deposits in South Africa. Commercially Ruthenium is isolated through a complex chemical process in which hydrogen is used to reduce ammonium ruthenium chloride yielding a powder. The powder is then consolidated by powder metallurgy techniques. Historically, Ruthenium was realized out of residues that were left after dissolving crude platinum. Ruthenium is a transition metal and as with most transition metals are excellent Lewis acids. That is they readily accept electrons from many molecules or ions that act as Lewis bases. When a Lewis base donates its electron pair to a Lewis acid, it is said to coordinate to the Lewis acid and form a coordinate covalent bond. When Lewis bases coordinate to metals acting as Lewis acids and form an integral structural unit, a coordination compound is formed. In this type of compound, or complex, the Lewis bases are called ligands and such ligands may be cationic, anionic or charge neutral.

Another portion of the Ruthenium complex of the present invention is a Polyoxometalates or “POM.” As a class, POMs are very functional for use as catalysts and are able to activate molecular oxygen and/or hydrogen peroxide as reagents in oxidation reactions. However, one of the major problems with using Ruthenium containing molecules as catalyst is the degeneration of the Ruthenium catalyst and the danger of Ruthenium poisoning to those in contact with the ions which may become dislodged/decomposed from the catalyst. The design of the filter material of the present invention overcomes these problems in part by using a uniquely designed siderophore, and in part by electrically charging the siderophore and nanocarbon tubules in contact with the siderophore.

The first screen of the repeating unit of the present invention comprises a boron doped synthetic carbon thin film and a charged plate bonded to the opposite side of the synthetic carbon film than the Ruthenium complex. Both the boron doped synthetic carbon thin film and the charged plate function synergistically as siderophores. A siderophore is a compound that will attract and bond free charged ions. In other words, a complex that will capture freely charged ions before the ions continue through the filter materials and out of the filter and into the airflow of a person. The siderophores of the present invention are negatively charged so as to be specific for positive charged ions including free Ruthenium ions. Thus, capturing any positive Ruthenium ions that may become dislodged from the diRuthenium/diRuthenium complex of the present invention overcomes the shortcomings of using Ruthenium as a catalyst for generating oxygen and therefore provides a safeguard against Ruthenium poisoning.

One embodiment of the present provides a filter material for splitting oxygen and/or hydrogen gas from a water source comprising a porous boron doped carbon film having diRuthenium/diRuthenium molecules and at least one type of electronegative ion attached either directly to the carbon film or, optionally, via an intermediate compound and/or structure. Whether the diRuthenium/diRuthenium molecules of the present invention are in direct contact with porous boron doped carbon film or are attached via an intermediate compound and/or structure, and is ionically, covalently and/or bonded via coordination complex bonding.

In one embodiment of the present invention, one diRuthenium molecule of each of the diRuthenium/diRuthenium molecules of the present invention has the following formula (I) [Ru₂(CO)₄(u-n²⁻O₂CR)₂L₂]_(x) wherein u is a bridging ligand selected from the group consisting of [Ru₂(EDTA)₂]²⁻, (CO)₄, F⁻, CO₃ ⁻², NO⁺ (Cationic), Hydrogen-bonded aromatic/carboxylic Acid-(either for multiple attachments as polymerization or singular, at the double bonded oxygen or sites within), ethylenediamine, halides as anionic ligands, carboxylic acid, unsaturated hydrocarbons, Nitric Acid coordinating to a metal center either linear or bent, butadiene, carboxylate ligands, anionic (RO— and RCO₂ ⁻² (wherein R is H or alkyl group) or neutral ligands (R₂, R₂S, CO, CN⁻), CH₃CN (Acetonitrile), NH₃ (Ammonia ammine) F⁻, Cl⁻, tris(pyrazolyl)borates as Scorpionate Ligand” a boron bound to three pyrazoles; the “pincers” of the compound refer to the nitrogen hetero atoms from two of the pyrazole groups (C₃H₄N₂) which can bind a metal) and mixtures thereof, preferably [Ru₂(EDTA)₂]²⁻;

wherein n is at least 2 and depends on the denticity of the molecule—(that is, the number of donor groups from a given ligand attached to the same central atom); wherein L is a ligand selected from the group consisting of [Ru₂(Ph₂PCH₂CH₂PPh₂)(EDTA)]²⁺, C₆H₆, R₂C═CR₂ (wherein R is H or an alkyl), 1,1-Bisdiphenylphosphino methane, diethylenetriamine [diene] bonds preferably tridentate, triazacyclononane [diene] bonds preferably tridentate, triphenylphosphine and mixtures thereof; wherein CR is carboxylic acid, carboxylate ligands, anionic (RO⁻ and RCO₂ ⁻ (wherein R is an alkyl group)) or neutral ligands (R₂, R₂S, CO⁻, CN⁻ (wherein R is an alkyl group)) and mixtures thereof;and x is about 1 to about 30, preferably 1 to about 20 and more preferably 1 to about 10.

The other molecule of the diRuthenium/diRuthenium molecules of the present invention is a diRuthenium-substituted polyoxometalate having the following formula (II) [WZnRu^(III) ₂ (OH)(H₂O)(ZnW₉O₃₄)₂] which can be converted to Ru₂Zn₂(H₂O)₂(ZnW₉O₃₄)₂ ⁻¹⁴ in the effective catalyst. The distance between each Ruthenium in the diRuthenium molecule is about 2.0 angstroms to about 3.0 angstroms, preferably about 2.25 angstroms to about 3.0, and more preferably about 2.50 angstroms to about 2.80 angstroms.

The di-Ruthenium-substituted polyoxometalates described in U.S. Pat. No. 7,208,244 to Shannon et al., the entirety of which is herein incorporated by reference, can be used in connection with the boron doped carbon thin film as described above so as to provide the benefits of the inventive filter material.

In yet another embodiment of the present invention, the filter material further comprises a Ruthenium ion capturing siderophore plate connected to the opposite surface of the first screen in which the diRuthenium/diRuthenium molecule is attached. The siderophore plate is ionically charged so as capture free Ruthenium ions that become dislodged from the porous boron doped carbon film. The siderophore plate can be selected from the group consisting of negative or positive charged ions, and resin clay in which the clay is molded into a hollow tubular plate having a plurality of pores. In particular, the siderophore plates can be polysulfinate impregnated resin plates, ethylenediaminetetraacetic acid (EDTA) containing plates and mixtures thereof.

In one embodiment of the present invention the siderophore plate is attached to one end of the nanotubules of the carbon doped film and at least a portion of the siderophore plate is directly attached and/or embedded into the thin film. This design allows the siderophore plate to be capable of capturing and ionically bonding free Ruthenium ions. As discussed above, this is essential when the filter material is used to produce oxygen for breathing. In an embodiment wherein oxygen produced by the filter material is not used for breathing but is used instead is used for an industrial process, the siderophore plate is less important.

In yet another embodiment of the present invention, the porous boron doped carbon film can further comprises a nanocarbon tubular mesh network. The nanotubules of the nanocarbon tubular mesh network have a diameter of about 20 nanometers to about 450 nanometers, preferable 20 nanometers to about 250 nanometers and more preferably about 20 nanometers to about 100 nanometers. The nanocarbon tubular mesh network is designed so that each tubule can carry current in extremely low resistance flow that is used to destabilize the oxygen-hydrogen bonds in water so as to make the hydrogen-oxygen bonds easier to split in order to produce bimolecular oxygen and/or hydrogen. According, the energy and the time necessary to split these bonds is less, thus making it quicker and easier to produce bimolecular oxygen. The nanotubular network extends above the supporting POM matrix by about 0.2 to about 5.0 microns.

Attaching the diRuthenium to the carbon thin film begins with the attachment of the carbon to a substrate. In one embodiment of the present invention a silicon substrate, or its like, is used to allow the carbon atoms from Chemical Vapor Deposition (CDV) to nucleate on the substrate surface initiating the tetrahedral coordinated Sp³ orbital network. The CDV use hydrogen and methane as precursor gases and use the “heated methodology”. The heated methodology, for example, can use a filament to provide the diffusion of the reactive species mostly “methyl radical” to interact with the substrate surface and allow the carbon atoms to be absorbed by the surface and growth coalescence to occur. Once complete, the thin-filmed surface is primarily tertiary carbon atoms with single C—H bonds.

The doping of the carbon thin film may be completed using boron, fluorine and/or nitrogen. With increased concentrations of the doping level the insulator behavior of the diamond alters to one of a semiconductor and further to a full metallic behavior, for electrochemistry the doping level has to be sufficient to cause a low ohmic drop in the diamond level, yet sufficiently low not to alter or disturb the crystalline structure inducing a graphite phase during the doping synthesis. In one embodiment of the invention, negative doping of the carbon is done with Fluorine as the negative ion, i.e., F⁻ the atom will have an extra electron and a slightly lower energy level. Approx 0.028-0.32 eV as opposed to Boron at 0.35 eV.

Typically the carbon-fluoride bond is covalent and very stable. Organofluorines may be safely used in applications such as drugs, without the risk of release of toxic fluoride. However use of fluorocarbon in an aromatic ring is useful but presents a safety problem: enzymes in the body metabolize some of them into poisonous epoxides. When the para position is substituted with fluorine, the aromatic ring is protected and epoxide is no longer produced. The substitution of hydrogen for fluorine in organic compounds offers a very large number of compounds. An estimated fifth of pharmaceutical compounds and 30% of agrochemical compounds contain fluorine. The —CF₃ and —OCF₃ moieties provide further variation, and more recently the —SF₅ group. Additionally in utilizing the born doped with the flourine atoms as

Boron trifluoride (BF₃) which prepared according to the following reaction:

B₂O₃+HF→2BF₃=3H₂0

Additionally, B₂O₃ and HF gas can be vaporized to inetract with the methane and fluorine containing compounds, such as, perfluoroalkyl-alkoxy silanes, with trifluoropropyl-trimethoxysilane (TFPTMOS) are preferred. No matter what flourine containing compounds that is used, it essential the fluorine containing compound has at least one carbon-metal bond per molecule.

The thin film produced functions as a Semiconductor as in this case of our shell composed of the Boron Doped Synthetic Diamond (carbon). The thin film is used as an anchor to the fluorine to diRuthenium sawhorse core molecule which functions as a semiconductor with inductive effects amplifying the electronegative moiety bonded to the sawhorse as the cationic species. Carbon in the diamond or grapheme structure is sp³ hybridized while the Boron (non carbon, i.e., non-diamond) is sp² hybridized. In the present invention this arrangement causes an electrical conductance in the thin film so as to be both an anchoring substrate while simultaneously functioning as a Hydroxyl radical for Oxygen generation electrode. The effective range of doping by Boron atoms is about 2100 ppm to about 6,800-ppm/0.1 cm of screen size.

In other words, in the present invention the boron doping atoms function as both electron acceptors form a band at about 0.35 eV above the valance band edge, at room temperature and some of the valance band electrons are promoted to the boron acceptors, leaving free electrons in the dopant band and holes vacancies in the valance band of the fluorine ion. Without such doping levels the diamond (carbon film) is a nonconductor or an insulator having large valence band gaps, i.e., the valance band to the conduction band that allows electric current to flow. In metals there is no band gap between valance and conduction band, as such control is lacking and ligand structure is exceedingly strained by repulsive forces of the ruthenium atoms in close proximity. However, in doping and use of the BDDSTF doping the carbon matrix sheet with boron/F-allows for conduction but under strained energies, this energy strain is conceptualized by the inventor as absorbing the repulsive energies between like Ruthenium atoms. Additionally the BDDSTF will slightly repel the end product Oxygen gas generated, therefore this shield functions as an ion-container itself, serving as an Oxygen reservoir much like the concept that uses multiple chambers to increase and secure the Oxygen content for patients breathing, as seen in the prior art.

The thin film produced functions as a semiconductor. In addition to its semiconductor effect, the screen composed of the boron doped synthetic diamond (carbon) thin film is used as anchor to keep the alignment of the Ruthenium complexes in the sawhorse orientation and to keep the POM from excessively separating and twisting when flows greater than 20 liters/min and/or water flows of greater than 4 liters/25 seconds are passed across the filter material of the present invention. Therefore, not only does the boron doped carbon thin film provide semiconductor properties, but it also functions to prevent the diRuthenium molecules from becoming distorted under high flows. In addition, the boron doped carbon thin film together with the fluorine causes an inductive effect that amplifies the electronegative moiety bonded to the sawhorse orientated Ruthenium complex as well as both inner sphere ligands while equally extending out to the diRuthenium-POM as outer sphere bonding.

The “Sawhorse molecule” can complex/bond to the to POM molecule either covalently, ionically and/or by coordination complexing. In particular, the bonding technique between the sawhorse molecule and the POM molecule is ionically-like bonded, since the complex uses the inductive effect from the F-attached to the Sawhorse in order to complex with POM. The inductive effect in chemistry is an experimentally observable effect of the transmission of charge through a chain of atoms in a molecule by electrostatic induction (IUPAC definition). The net polar effect exerted by a substituent is a combination of this inductive effect and the mesomeric effect. The electron cloud in a s-bond between two unlike atoms is not uniform and is slightly displaced towards the more electronegative of the two atoms. This causes a permanent state of bond polarization, where the more electronegative atom (in our case the F⁻ has a slightly negative charge (d−) and the other atom has a slight positive charge (d+). If the electronegative atom (F—) is then joined to a chain of atoms, usually carbon (O₂RC derivatives of carboxylic acid at ligand points in the sawhorse), the positive charge is relayed to the other atoms in the chain (across the Sawhorse to the POM giving an electron-withdrawing inductive effect, also known as the —I effect.)

If a purely “ionic bonded Sawhorse to POM species” is used in the present invention, then additionally known bridging ligands between the Ruthenium Sawhorse core is offered as the anion [Ru₂(EDTA)₂]²⁻[Ru₂(EDTA)₂]²⁻ and the bridging ligand is used as the cation (such as [Ru₂(Ph₂PCH₂CH₂PPh₂)(EDTA)]²⁺) which can then be linked by forming an amide with triethylene diamine, H₂NCH₂CH₂CH₂NH₂. This is used both as the specific ligand to bind the two molecule core and Ruthenium Substituted Polyoxometalate (RPOM), WZnRu₂ ^(III)(OH)(H₂O(ZnW₉O₃₄)₂]¹¹. This done so as to a) not decimate the sawhorse molecule, and B) to contribute to the electro-generating capabilities for generating high purity (>97%) Oxygen as end product. This can be achieved by the close proximity of additional ruthenium atoms, even under great repulsive strain, which is not the case when a metal carbide intermediary is used.

The carbon in the diamond or graphite structure is sp³ hybridized while the Boron (non carbon, i.e., non-diamond) is a sp² species. The specific hybridization states of the carbon and boron discussed above are important in providing electrical conductance to the thin film so that the thin film functions as both an anchoring substrate and an oxygen-generating electrode. In order to be effective for the stated purpose above, the thin film must be boron doped in a range between about 2100 ppm to about 6,800-ppm/0.1 cm of thin film (screen) size.

The second screen of the repeating unit of the present invention further comprises a synthetic film having a plurality of nanocarbon tubules attached and/or embedded thereon to form a nanocarbon tubule mesh network. The synthetic film of the present invention is selected from the group consisting of SiO₄, AlO₄, and mixtures thereof. The crystal structure of zeolites typically is based upon repeating units consisting of a silicon atom (+4 valence) surrounded by four oxygen atoms (−2 valence) in a tetrahedral configuration. Two Si atoms, giving the tetrahedral net valence of zero, share an oxygen molecule. When aluminum (with a valence of +3) is substituted in the tetrahedral orientation, a net charge—1 occurs and thus gives rise to the cation exchange properties of zeolites (further discussed below). The synthetic film is positioned proximal to the surface of the porous boron doped carbon film in which the siderophore is attached. The synthetic film of the present invention further comprising at least one zeolite crystalline body that is in direct contact with the nanocarbon tubule mesh network attached and/or embedded thereon. The synthetic film has a multiplicity of pores with a diameter of about 0.1 to about 3.4 nm, preferably about 0.1 nm to about 3.0 nm and more preferably about 2.0 nm to about 2.9 nm.

Zeolites typically are hydrated aluminosilicate minerals having micro-porous structures. Accordingly, the synthetic zeolite synthetic film of the present invention operates as a molecular sieve where the maximum size of the molecular or ionic species that can enter the pores of a zeolite is controlled by the diameters of the tunnels in the seive that are conventionally defined by the ring size of the aperture. For example, a zeolite complex having an 8-ring struture is a closed loop built from 8 tetrahedrally coordinated silicon (or aluminum) atoms and 8 oxygen atoms and itself comprises a multiplicity of pores. In other words, the size of the apertures in the zeolite synthetic film that controls entry of the particular ions into the internal pore volume of the zeolite synthetic film is determined by the number of T atoms (T=Si or Al) and oxygen in the ring. The apertures are classified as ultra large (>12 membered ring), large (12), medium (10) or small (8). Aperture sizes range form about 0.4 nm for an 8 ring structure such as zeolite A, about 0.54 nm for a 10 ring structure such as ZSM-5 and about 7.4 nm for a 12 ring structure such as zeolite X and ZSM-12, all of which can be used in the present invention.

The synthetic film itself comprises a multiplicity of pores having a diameter of about 0.1 to about 3.0 nm providing an oxygen sieving effect (0₂=2.96 A° and N₂=3.16 A°). The zeolite crystalline bodies attached to the nanocarbon tubules overlap at least part of the pores. The porous boron doped carbon film comprising diRuthenium/diRuthenium molecules together with the thin synthetic film having carbon nanotubules attached and zeolite crystalline bodies in direct contact with the nanocarbon tubules form a repeating unit that can be used to make up the filter material of the present invention.

Zeolites used in the present invention have a crystal structure constructed from a TO₄ tetrahedral configuration, where T is either Si or Al. In addition to a large number of naturally occurring zeolites, there is a wide range of synthetic zeolites as well. As stated above, the crystal structure of zeolites is based upon repeating units consisting of a silicon atom (+4 valence) surrounded by four oxygen atoms (−2 valence) in a tetrahedral configuration. Each oxygen atom is shared by two Si atoms, giving the zeolite its tetrahedral structure and a net charge of zero. When aluminum (with a valence of +3) is substituted in the tetrahedral configuration the zeolite will have a net charge of −1. This negative charge gives rise to the cation exchange properties of zeolites. Zeolites also have very uniform defined pore sizes as well as high porosity, which occur as a consequence of their unique crystal structures. For this reason, zeolites are useful as molecular sieves.

In one embodiment of the present invention, the zeolite crystalline bodies used in the second and third screens of the present invention are directly attached to the nanocarbon tubules of the nanocarbon tubule mesh network so that the zeolite crystalline bodies overlap at least part of the pores in the synthetic film. This configuration allows oxygen and/or hydrogen generated from the reaction of water molecules with the zeolite/nanotubules (and diRuthenium complex described above) to flow through the pores of the synthetic film to be collected and used for a given purpose. It is the combination of the diRuthenium/diRuthenium containing porous boron doped carbon film and the synthetic film containing zeolite crystalline bodies attached to the nanocarbon tubular mesh network overlapping at least part of the pores in the synthetic film that forms a repeating unit of the filter material of the present invention.

However, un-split water frequently blocks the pores of certain zeolites and therefore often these zeolites often become fouled and loss their separation qualities. The structure of the filter material of the present invention allows the zeolites attached to the tubular mesh network to remain “unclogged” and functional for a longer period of time because the nanotubules of the present filter material destabilizes the hydrogen/oxygen bond in water thereby making it easier for the diRuthenium molecules of the filter material to split water into oxygen and hydrogen. The more water that is split by the diRuthenium molecules, the more oxygen/hydrogen is generated and the less water available to clog the pores of the zeolite attached to the nanotubules of the synthetic film of the present invention. Once the oxygen and/or hydrogen are generated it can be captured and used for breathing, storage or industrial uses.

The pore size of the zeolites used is also critical. If the pores are too large water can pass through the zeolite filter and not be filtered to oxygen and hydrogen, too small the oxygen and/or hydrogen produced can be retained and not passed out of the filter so that they can be utilized. Therefore, it is important that it is possible to fine-tune the pore opening of zeolites so as to allow the adsorption of specific molecules while excluding others based on size. One method to change the pore size of the zeolite is to change the exchangeable cation from one cation to another. For example, when Na+ ions are replaced by Ca++ ions in zeolite A, the effective aperture size increases. This can also be accomplished by changing the Al/Si ratio in the zeolite. An increase in the ratio of Si to Al will slightly decrease the unit cell size, decrease the number of exchangeable cations, thus freeing the channels and make the zeolite more hydrophobic in character.

Preferred zeolites used in the present invention are mainly composed of alumin-silicates wherein the alumina substrate contains alumina pores that function as molecular sieves that allow some atoms to pass through but excludes others so produce a chosen end product. For purpose of this application the term “molecular sieve” refers to a particular property of selectively sorting molecules based primarily on a size exclusion process. The zeolites that can be used in the present invention include any one of a family of hydrous aluminum silicate minerals, typically alkali metals and alkaline earth metals whose molecules enclose cations of sodium, potassium, calcium, strontium, or barium, or a corresponding synthetic compound.

The nanocarbon tubular mesh network embedded on the surface of the synthetic film extends about 0.1 to about 7 millimeters above the surface of the zeolite coating synthetic film, preferably about 0.2 to about 6 millimeters and more preferably about 0.2 to about 5 millimeters. As with the nanotubules associated with the diRuthenium containing carbon-doped film, the nanocarbon tubules can have a diameter of about 20 nanometers to about 450 nanometers. The nanocarbon tubular mesh network can be embedded on the surface of the synthetic film using electron-beam lithography, atomic force microscopy, chemically charged molecular ink, crystallization self-assembly, seeded self-assembly, and/or mixtures as well as any other procedure that does not affect the pores of the synthetic film to which it is embedded.

One method that can be used to assure that the filter material of the present invention has the proper arrangement is direct visualization during the embedding process by “IBM Almaden's Materials Characterization and Analysis Lab,” which uses a FEI 830 Dual Beam system that integrates the FIB (Focused Ion Beam) with a ultra-high-resolution SEM. The methods allow the analyst to capture an image of a specific site while performing a milling or deposition procedure. In making the carbon thin film, the thin film is first milled by accelerated gallium ions so as to dig the initial hole for the nanocarbon tubules to be embedded with the born doped thin film. Once completed, a carbon metal oxide is deposited within the milled region to form a pattern and underside of the carbon tubules while an inert gas, such as Argon, is pumped onto the surface of the thin film. Additional carbon doped atoms are deposited onto the argon gas surface above the nanocarbon tubule concavity previously formed in the thin film by the gallium ions. The deposition may be completed either by ALD (atomic Layer Deposition) or CVD so that the carbon tubules are laid down in a concentric pattern extending from the innermost point of the thin film outward. Once carbon nanotubule is completed, the end portion of the carbon nanotubule is left open so that current can be applied within the carbon nanotubules. The diRuthenium molecules are then either aerosolized onto the prepared surface or applied using CVD so as to bond with the boron fluorine at the newly prepared thin film surface.

In the alternative, the method used to form the Carbon Boron doped Fluoride film could be by radio frequency magnetron sputtering using a composite target consisting of h-BN and graphite in an Ar—F₂ gas mixture, The Ar—F₂ gas mixture formed by photolysis of hydrogen fluoride in a solid argon matrix leads to the formation of argon fluorohydride (HArF). Subsequent to the formation, the carbon doped fluoride thin film may be characterized by X-ray diffraction, Fourier transform infrared spectroscopy and/or X-ray photoelectron spectroscopy. Descriptions of these procedures can be found in Preparation of boron carbon nitride thin films by radio frequency magnetron sputtering, Applied Surface Science, Volume 25Z Issue 12, 15 Apr. 2006, Pages 4185-4189. Lihua Liu, Yuxin Wang, Kecheng Feng, Yingai Li, Weiqing Li, Chunhong Zhao, Yongnian Zhao; and A stable argon compound. Leonid Khriachtchev, Mika Pettersson, Nino Runeberg, Jan Lundell & Markku Räsänen. Department of Chemistry, PO Box 55 (A.I. Virtasen aukio 1), FIN-00014 University of Helsinki, Finland. Nature 406, 874-876 (24 Aug. 2000).

The di-ruthenium thin film screen and the zeolite synthetic film can be arranged in concentric spaced circles starting form the center region of the either the porous boron doped carbon film or the zeolite synthetic film outwards.

Overall the first and second screens of the repeating units in the first chamber of the present invention are designed so that the zeolite synthetic film screen is placed proximal to the diRuthenium boron doped thin film screen so that the diRuthenium screen is proximal to the air flow, i.e., the airflow contacts the diRuthenium screen first. In this way moisture contained in the airflow (and/or provided from an external source) is electrochemically aided to enhance the splitting of water into oxygen and hydrogen and the second screen functions to filter out the generated oxygen/hydrogen from the splitting of water. The zeolite and diRuthenium screens function in tandem while the third screen regenerates hydrogen peroxide from hydrogen and oxygen. The diRuthenium center and outer border sandwiching the zeolite center bonded to and surrounded by diRuthenium walls of the repeating units can be analyzed postproduction by FTIR and or X-ray crystallography for its accuracy and bonded interface.

Specific embodiments of the present invention are described in conjunction with the attached figures in order to better describe the invention and should not be regarded as limiting the present invention in any way.

FIG. 1 shows a prospective view of the front surface of the porous boron doped carbon film comprising diRuthenium/diRuthenium molecules of the filter material of the present invention (10). As stated above and shown in FIG. 1, the mesh-like material in which the screen is made of is a carbon boron doped screen (15) having a top (55), a bottom (60), a right side (45) and a left side (50). Alternative shapes such as circular, oval, elliptical, parallelograms in particular, square, rectangular and triangular are also within the scope of the invention.

FIG. 1 shows a rectangular screen for description purposes only but other shapes are envisioned to fall within the scope of the present invention. Deposed or embedded on/in the carbon boron doped screen (15) are nanocarbon tubules (20) that originate from a central point in the screen and radiate outwards to form a loosely packed coil structure in a concentric arrangement. Although the nanocarbon tubules are concentrically arranged, in the alternative the carbon nanotubules can be arranged in different patterns depending on the design and shape of the carbon boron doped screen (15). The different arrangements of the nanotubules, as with the different shapes of the screen, are also envisioned to fall within the scope of the invention.

Dispersed throughout the carbon boron doped screen (15) are numerous boron atoms (25). These boron atoms (25) can be evenly dispersed throughout the screen or may be concentrated within the area of the nanocarbon tubules. Approximately in the center region of the nanocarbon screen (15) is at least one diRuthenium-substituted polyoxometalate (POM) complex (40). As described above, in one embodiment of the present invention the diRuthenium-substituted polyoxometalate (POM) complex (40) comprises a diRuthenium sawhorse molecule (35) attached to a POM (30). The diRuthenium sawhorse molecule (35) is located closet to the screen while the POM (30) extends out of the face of the screen. This arrangement allows for quick and efficient degradation of water into bimolecular oxygen and hydrogen. This arrangement makes up the structural arrangement of the first screen of the repeating unit of the filter material of the present invention.

FIG. 2 shows a prospective view of the back surface of the porous boron doped carbon film (100) comprising diRuthenium/diRuthenium molecules and a siderophore (115). The carbon boron doped screen of the invention has a top (105), bottom (110), a left side (120) and a right side (125). The siderophore (115) is shown in FIG. 2 as being located at the bottom (110) of the screen, however, it is within the scope of the invention for the siderophore (115) to be located in other portions of the screen depending on the shape of the screen and the arrangement of the nanotubules. The carbon boron doped screen (15) contains boron atoms (25) as well as carbon nanotubules (20) and at least one diRuthenium-substituted polyoxometalate (POM) complex (40) as shown in FIG. 1 and discussed above.

The siderophore (115) can be in the form of a hollow tubular structure having a plurality of pores wherein at least one end of the siderophore (115) is in direct communication with at least one end of the nanocarbon tubules. In the alternative, the siderophore (115) can be in the form of an ionically charged plate. Either configuration is designed to capture charged ions such as, ruthenium ions that may become dislodged from the filter material so as to protect a patient breathing the oxygen produced by the filter material from inhaling the free ruthenium ions. Either the plate or the hollow tube siderophore (115) can be constructed from impregnated polysulfinate resin, ethylenediaminetetraacetic acid (EDTA) and mixtures thereof.

FIG. 3 shows a prospective view of the surface of the synthetic film comprising zeolite crystalline bodies of the present invention (200). This is the next screen in the repeating unit of the filter and is positioned facing the back surface of the boron doped carbon film having the siderophore shown in FIG. 2. The synthetic film (200) has a top (205), a bottom (210), a right (220) and a left (225) side and is shown in a rectangular configuration. As with the first screen, the synthetic screen is shown in a rectangular shape but alternative shapes such as circular, oval, elliptical, parallelograms in particular, square, rectangular and triangular are envisioned to fall within the scope of the invention. That is, FIG. 3 shows a rectangular screen for description purposes only but other shapes fall within the scope of the present invention.

As with the boron doped carbon film of FIGS. 1 and 2, the synthetic film of FIG. 3 has carbon nanotubules (215) embedded or deposed thereon. The synthetic screen also has zeolite crystalline bodies (240) in direct contact with the nanotubules (215), in direct contact with the synthetic film or in direct contact with both.

FIG. 4 shows a prospective view of the surface of the third screen (300) comprising zeolite crystalline bodies and diRuthenium/diRuthenium molecules of the present invention. This is a combination of the diRuthenium/diRuthenium complex ((40) of FIG. 1) and the zeolite ((240) shown in FIG. 3) deposed/embedded in the synthetic screen of FIG. 3. The third screen (300) can optionally included a siderophore plate (115) to capture any free ruthenium ions that may dislodged from the screen. The third screen (300) is designed so as to produce hydrogen peroxide from hydrogen and oxygen.

FIG. 5 shows a prospective view of the front surface of the second screen comprising zeolite crystalline bodies set in a frame (130) The second screen/frame (130) of the repeating unit of the present invention comprises a frame (135) that is both structural and functions as a hollow tubular passage of gases to different regions of the filter screen. The frame is equipped with several blow-by nozzles (145) having a wide end (155) and a narrow end (140). The wide end (155) of the blow-by nozzles is connected to the frame (135) wherein the narrow end (140) extends over the zeolite crystalline screen (170). As air, either exhaled from the patient, taken from the atmosphere or produced from a fan motor (shown in FIG. 6), passes into the frame (135) at least a portion of the air passes through the wide end of the blow-by nozzle (155) so as to exit the narrow end (140) positioned over the zeolite crystalline screen (170). It is from this air that oxygen is adsorbed from constituents gases contained in air and is added to the oxygen, and hydrogen split from water from the catalyst screen.

The frame (140) is also equipped with scavengers (175) having a narrow end (180) that is attached to the frame (140) and a wide end (185) that extends over the zeolite crystalline screen (170). As described above, this specific configuration of the scavengers (175) allows for oxygen, excess water, excess gases, built up surface electrostatic charges, as well as waste gases that do not pass through the screen to be drawn into the wide end (185) of the scavengers (175) and into the frame (135) to be either collected and/or exhausted from the filter material. The specific design of the scavengers, having the wide end (185) positioned over the screen across from the blow by nozzles (145) and the narrow end (180) attached to the frame (140), where at this site in the frame a designed constriction accelerates the airflow which facilitates a suction into the scavenger nozzles that is able to draw in gases as described above.

The blow-by nozzles (145) are also specifically designed so as to propel the incoming air out of the nozzles (145) across the screen (170). That is, the wide end (155) of the blow-by nozzles (145) is attached to the frame (140) so that the path of the air entering the blow-by nozzles (145) is constricted to the narrow end (140), which exits out over the screen (170). The constricted path causes the airflow exiting over the screen to exit at a higher acceleration than when it enters. The frame (130) is also equipped with a first connection (150) and a second connection (190) that is designed to connect to with the bifurcated accelerator described above and shown in FIG. 6. As with the filter shown in FIG. 3, the synthetic film (170) has the same components shown therein, namely nanotubules (165) arranged in a concentric arrangement with zeolite atoms (160) associated therewith. A feed tube (shown in FIG. 6 can be attached to the frame (135) at points (150) and (190).

The boron doped carbon first screen of the repeating unit having the diRuthenium complex (40) shown in FIGS. 1 and 2 is also arranged in a frame as shown in FIG. 5 above. That is, the boron doped carbon screen shown in FIGS. 1 and 2 is set in a frame having scavengers and blow-by nozzles as described above and shown in FIG. 5 and is part of the repeating unit of the filtering material of the present invention.

FIG. 6 shows a prospective view of the front surface of the screen with a flow tube (305) connected (305) to the frame of the screen of the present invention. The flow tube (305) has a main feed tube (355) that bifurcates to a first junction (310) and a second junction (315). The first junction (310) is connected to frame attachment point (335) that is configured so that air/fluid flow exiting this first junction (310) flows to the scavenger nozzles shown in FIG. 5. The second junction (315) is attached to frame connection point (330), which is configured so that air/fluid flow exiting the second junction (315) flows to the blow by nozzles (355). The blow-by nozzles (355) are designed so as to further accelerate the flow of air as it exits across the surface of the synthetic film. This same configuration is used with the first screen shown in FIGS. 1 and 2.

FIG. 7 shows a cross section view of a cartridge with a flow tube (305) connected to the frame of the screens of the present invention. Flow tube (305) feeds junction (310) and a second junction (315) which are designed to connect to the first and second screens of the repeating units of the present invention. The screens (410) can be encased in an overall frame (415) which ultimately fits into a cartridge housing (405). Other configurations are possible and fall with the scope of the invention.

FIG. 8 shows a prospective view of the housing assembly (450) of the present invention.

FIG. 9 shows the housing assembly (500) having a first chamber (505) and a second chamber (510) separated by a separator (515). Attached to the housing assembly (500) is a drive motor (525) configured so as to operate a fan (520), a first pump (545) and a second pump (540). Attached to the fan is an air tube (560) that extends into the first chamber (505) and is configured to have a plurality of extensions designed to provide air to each of the screens in the repeating units (585). One repeating unit (585) is shown in the first chamber (505) for illustrative purposes only, since in practice several repeating units would be arranged in series. Depending on the amount of oxygen required, the number of repeating units can vary from 1 to about 100 and can range in size from about 1 inch to several feet.

As shown in FIG. 9, a first pump (540) and a second pump (545) are configured so as to be driven by the same drive motor (525) that operates the fan (520). In the alternative, separate drive motors can be provided to drive each or both of the pumps (540, 545). The first pump (540) is in communication with an exhaust tube (535) that extends into the first chamber (505), through the separator (515), and into the second chamber (510). The exhaust tube (535) is configured with a plurality of pores (565) disposed throughout the length of the exhaust tube (535) so as to draw oxygen and/or hydrogen produced in each chamber into the exhaust tube (535) and out of the housing assembly. The exhaust tube (535) can vent directly into the environment, into a breathing device, into an extraterrestrial suit or breathing device, or into a storage vessel for future use.

In one embodiment of the present invention, the exhaust tube (535) is in direct communication with the first pump (540). When the pump is activated, suction is generated in the exhaust tube (535) which draws gases into the tube from the first and second chambers. As stated above, in order to facilitate the up take of these gases the exhaust tube (535) is configured with multiple pores (565) dispersed throughout the length of the exhaust tube (550). The first pump (540) can be a pneumatic or centrifugal pump.

The housing assembly is also configured with a hydrogen peroxide supply tube (556) and a water supply tube (555) that extends into the chambers of the housing assembly. The hydrogen peroxide supply tube (556) extends through the first chamber (505), through the separator (515) and into the second chamber (510). In the second chamber (510) the hydrogen peroxide supply tube (556) terminates at a hydrogen peroxide distribution feed (570). The hydrogen peroxide distribution feed (570) is configured to have a plurality of spray nozzles (630) that spray hydrogen peroxide about the second chamber (510). The hydrogen peroxide feed (556) can be configured as a hollow linear tube or in a circular ring having spray nozzles.

The water supply tube (555) extends into the first chamber (505) and terminates at a water distribution feed (605). The water distribution feed (605) is configured to have a plurality of spray nozzles (635) that spray water about the first chamber (505) onto the screens in the repeating units (585). The water is then split into bi-molecular oxygen and hydrogen which is released into the first chamber (505) and drawn into the gas exhaust tube (535) where it is vented out of the housing assembly (500).

Both the hydrogen peroxide supply tube (556) and water supply tube (555) are in direct communication with the second pump (545). When the second pump is activated hydrogen peroxide is pumped from a hydroxide peroxide supply, into the hydrogen peroxide supply tube (556) and then into hydrogen peroxide distribution feed (570) where it is released into the second chamber (510). Once released into the second chamber (510), the hydrogen peroxide reacts with the catalyst (580) embedded in the walls of second chamber (510).

In one embodiment of the present invention, the catalyst embedded in the walls of second chamber (510) is MnO₂ and produces oxygen upon contact with hydrogen peroxide. The rate of oxygen production is proportional to the loading of catalyst in the wall of the second chamber and the amount of hydrogen peroxide added to the chamber.

Similarly, when the second pump (or in the alternative a separate pump) is activated, water is pumped from a water supply into the water supply tube (555) and then into water distribution feed (635) where it is released into the first chamber (505). Once released into the first chamber (505), the water reacts with the screens in the repeating units (585) as described above. The water supply can be replenished from the atmosphere, from the filtration of urine or in the alternative from a chemical reaction where water is a by-product.

As described above the third screen of the repeating units produce hydrogen peroxide from oxygen and hydrogen. Once the hydrogen peroxide is produced it exits the repeating units and accumulates on the first chamber side of the separator (515). The separator (515) can be arranged at a slight tilt so that the hydrogen peroxide exiting the repeating units (585) accumulates at one end of the separator surface. A one-way flap valve (575) that opens into the second chamber from the first chamber is positioned in the separator in the vicinity of the lowest point of the tilted separator (515). As hydrogen peroxide accumulates at the lowest point of the separator, the one-way flap valve (575) opens towards the second chamber (510) to allow hydrogen peroxide to drip into the second chamber. Once in the second chamber the hydrogen peroxide reacts with the catalyst to produce bimolecular oxygen and hydrogen. The hydrogen produced can be used to supply a hydrogen fuel cell to provide energy to the drive motor or other parts of the apparatus. It is essential that the flap valve is a one-way valve that opens into the second chamber so that hydrogen peroxide does not back flow into the first chamber should zero gravity conditions arise or if the canister is turned over.

FIG. 10 shows and exploded view of the repeating unit (585) comprising three screens (605, 610, and 615) and their arrangement in the repeating unit of the invention.

The present invention is also directed to a method for producing bimolecular oxygen and/or hydrogen in a rarified atmosphere using of the invention described above.

While the above description contains many specifics, these specifics should not be construed as limitations of the invention, but merely as exemplifications of preferred embodiments thereof. Those skilled in the art will envision many other embodiments within the scope and spirit of the invention as defined by the claims appended hereto. 

1. An apparatus for producing oxygen in an environment substantially devoid of oxygen comprising; a housing; said housing separated into a first chamber and second chamber; said first chamber comprising a catalytic filter material comprising a plurality of repeating units, said repeating unit comprising: a first screen comprising a porous boron doped carbon film comprising diRuthenium/diRuthenium molecules and at least one type of electronegative ion, said diRuthenium/diRuthenium molecules and said electronegative ions in direct contact with said porous boron doped carbon film, said porous boron doped carbon film further comprising a nanocarbon tubular mesh network and a Ruthenium ion capturing siderophore; a second screen comprising a synthetic film comprising a plurality of nanocarbon tubules attached and/or embedded to/on a surface of said synthetic film to form a nanocarbon tubule mesh network and at least one zeolite crystalline body in direct contact with said nanocarbon tubules wherein said synthetic film comprises a multiplicity of pores having a diameter of about 0.1 to about 3.0 nm and said zeolite crystalline attached to said nanocarbon tubules overlap at least part of said pores; a third screen comprising a synthetic film comprising a plurality of nanocarbon tubules attached and/or embedded to/on a surface of said synthetic film to form a nanocarbon tubule mesh network and zeolite and diRuthenium/diRuthenium molecules positioned in close communication with said surface of said synthetic film for generating hydrogen peroxide; and said second chamber comprising a catalyst for generating oxygen upon contact with an oxygen generating liquid.
 2. The apparatus of claim 1 wherein said catalyst in said second chamber is selected from the group consisting of manganese dioxide, silver and mixtures thereof and said oxygen generating liquid is hydrogen peroxide.
 3. The apparatus of claim 2 wherein said catalyst is manganese dioxide and is embedded in an internal surface of said second chamber.
 4. The apparatus of claim 3 wherein the first, second and third screens of the repeating units of said first chamber further comprise a partially hollow frame.
 5. The apparatus of claim 4 further comprising a plurality of blow-by accelerator nozzles in communication with said frame, said blow-by nozzles configured so that air from said blow-by nozzles flows over the surface of said; and a plurality of scavenger nozzles in communication with said frame, said plurality of scavenger nozzles positioned substantially across from said plurality of blow-by nozzles whereby a combination of un-reacted air flow and by-products from said blow-by nozzles that flows over the surfaces of said screens is captured by said scavenger nozzles and channeled into said frame to be used and/or vented out of said apparatus.
 6. The apparatus of claim 5 wherein said blow-by accelerator ports have a wide end attached to said frame and a narrower end positioned at least partially over said porous boron doped carbon film so that air from said blow-by accelerator ports flows over said porous boron doped carbon film.
 7. The apparatus of claim 6 wherein said scavenger ports have a narrow end attached to said frame and a wide end positioned at least partially over said porous boron doped carbon film so that un-reacted air flow and by-products from said blow-by accelerator ports is captured by said scavenger ports and channeled into said frame to be used and/or vented out of said apparatus.
 8. The apparatus of claim 7 wherein one diRuthenium molecule of each said diRuthenium/diRuthenium molecule of said porous boron doped carbon film of said repeating units has the following formula (I): [Ru₂(CO)₄(u-n ²⁻O₂CR)₂L₂]_(x)  (I) wherein u is a bridging ligand selected from the group consisting of [Ru₂(EDTA)₂]²⁻, (CO)₄, F⁻, Co₃ ⁻², NO⁺ (Cationic), Hydrogen-bonded aromatic/carboxylic Acid-(either for multiple attachments as polymerization or singular, at the double bonded Oxygen or sites within), ethylenediamine, halides as anionic ligands, carboxylic acid, unsaturated hydrocarbons, Nitric Acid coordinating to a metal center either linear or bent, butadiene, carboxylate ligands, anionic (RO— and RCO₂ ⁻² (wherein R is H or hydrocarbon) or neutral ligands (R₂, R₂S, CO, CN⁻), CH₃CN (Acetonitrile), NH₃ (Ammonia ammine) F⁻, Cl⁻, tris(pyrazolyl)borates and mixtures thereof, preferably [Ru₂(EDTA)₂]²⁻; wherein n is at least 2 and depends on the denticity of the molecule—(that is, the number of donor groups from a given ligand attached to the same central atom); wherein L is a ligand selected from the group consisting of [Ru₂(Ph₂PCH₂CH₂PPh₂)(EDTA)]²⁺, C₆H₆, R₂C═CR₂ (wherein R is H or an alkyl), 1,1-Bisdiphenylphosphino methane, diethylenetriamine [diene] bonds preferably tridentate, triazacyclononane [diene] bonds preferably tridentate, triphenylphosphine and mixtures thereof; wherein CR is carboxylic acid, carboxylate ligands, anionic (RO⁻ and RCO₂ ⁻ (wherein R is an alkyl group)) or neutral ligands (R₂, R₂S, CO⁻, CN⁻ (wherein R is an alkyl group)) and mixtures thereof; and x is between 1 and about
 30. 9. The apparatus of claim 8 wherein one diRuthenium of said diRuthenium/diRuthenium molecules of formula (I) is attached to a diRuthenium-substituted polyoxometalate having the following formula (II) [WZnRu^(III) ₂(OH)(H₂O)(ZnW₉O₃₄)₂]  (II).
 10. The apparatus of 1 wherein said siderophore plate is selected from the group consisting of a polysulfinate resin impregnated plate, ethylenediaminetetraacetic acid (EDTA) and mixtures thereof.
 11. The apparatus of claim 10 wherein the distance between each Ruthenium in said diRuthenium/diRuthenium is about 2.75 angstroms.
 12. The apparatus of 11 wherein said nanotubules of said nanocarbon tubular mesh network have a diameter of about 20 nanometers to about 450 nanometers.
 13. The apparatus of claim 12 wherein said synthetic film is SiO₄, AlO₄, and mixtures thereof.
 14. The apparatus of 13 wherein said nanocarbon tubular mesh network embedded on said surface of said synthetic film extends about 0.2 to about 5 millimeters above said surface.
 15. The apparatus of claim 14 wherein said nanocarbon tubular mesh network is arranged in concentric spaced circles starting form a center region of said porous boron doped carbon film outwards.
 16. The apparatus of 15 wherein nanocarbon tubules embedded on said surface of said zeolite containing synthetic film is arranged in concentric spaced circles starting form a center region of said porous boron doped carbon film outwards.
 17. The apparatus of claim 1 wherein said cartridge is removable from said apparatus and further comprises an insert for a removable cartridge case, said cartridge case configured to have a plurality of slots and a void extending from one side of said cartridge case to the other wherein said plurality of slots are configured to accommodate said repeating units and said void is configured so as to leave at least a portion of said filter material exposed to said source.
 18. The apparatus of claim 8 wherein said diRuthenium-substituted polyoxometalate of formula (II) is Na₁₄[Ru₂Zn₂(H20)₂(ZnW₉O₃₄)₂].
 19. A breathing device for breathing in atmospheres substantially void of oxygen comprising said apparatus of claim
 1. 20. The breathing device of claim 19 further comprising a filter for producing water from the urine of a mammal, said filter in fluid communication with said filter chamber whereby water vapor produced from the purification of urine flows over said filter to produce breathable oxygen.
 21. A method for producing bimolecular oxygen in an atmosphere substantially devoid of oxygen comprising: utilizing said breathing device of claim 19 wherein water vapor from a water reserve, the atmosphere and/or exhaled air flows into said first chamber to react with said repeating units so as to produce oxygen and/or hydrogen gas.
 22. The method of claim 21 wherein water vapor from said filter for producing water from urine also flows into said first chamber to react with said repeating units so as to produce oxygen and/or hydrogen gas. 